Accurate Modeling of Bromide and Iodide Hydration with Data-Driven Many-Body Potentials

Ion–water interactions play a central role in determining the properties of aqueous systems in a wide range of environments. However, a quantitative understanding of how the hydration properties of ions evolve from small aqueous clusters to bulk solutions and interfaces remains elusive. Here, we introduce the second generation of data-driven many-body energy (MB-nrg) potential energy functions (PEFs) representing bromide–water and iodide–water interactions. The MB-nrg PEFs use permutationally invariant polynomials to reproduce two-body and three-body energies calculated at the coupled cluster level of theory, and implicitly represent all higher-body energies using classical many-body polarization. A systematic analysis of the hydration structure of small Br^–(H₂O)_n and I^–(H₂O)_n clusters demonstrates that the MB-nrg PEFs predict interaction energies in quantitative agreement with “gold standard” coupled cluster reference values. Importantly, when used in molecular dynamics simulations carried out in the isothermal–isobaric ensemble for single bromide and iodide ions in liquid water, the MB-nrg PEFs predict extended X-ray absorption fine structure (EXAFS) spectra that accurately reproduce the experimental spectra, which thus allows for characterizing the hydration structure of the two ions with a high level of confidence.